Pesticidal methods employing halogenated polycyclic sultones



United States Patent This application is a division of my application S.N. 231,282, filed October 17, 1962, now U.S. Patent No. 3,201,417.

This invention relates to pesticidal methods utilizing new halogenated polycyclic sultones, such as are obtainable by reaction of a hexahalobicyclo(2.2.1)heptadiene with sulfuric anhydride o-r oleum.

The reactions of oleum or sulfuric acid with highly halogenated cyclic hydrocarbons have been known to produce polyhalogenated ketones with concomitant release of hy-' drogen halide. Therefore, such are unexpected in that they proceed substantially without evolution of hydrogen halide and yield sultones.

It has now been found that the reaction of a hexaholobicyclo(2.2. l heptadiene of the structure:

where X is halogen, preferably chlorine, where A and B are carbon atoms, where D is a radical chosen from the group consisting of hydrogen, alkyl, and alkylidene radicals, and where E is a radical chosen from the group consisting of hydrogen and alkyl; A and B being connected by a double bond when D is monovalent (hydrogen or alkyl) and by a single bond when D is divalent (alkylidene), with a compound chosen from the group consisting of sulfuric anhydride and oleum, yields a sultone having the empirical formula identical to the empirical formula of the organic starting material plus the elements of sulfur trioxide.

The radicals D and E may be alkyl groups of any chain length, but lower alkyl, i.e., up to eight carbons, is preferred. Likewise, D may be an alkylidene radical of any length, branched or unbranched, but lower alkylidene, up to eight carbon atoms, is preferred. Suitable starting materials and the products formed therefrom include the following:

Patented May 31, 1966 (Ll 0 Ha C1 c1 oH,

H CClz E 0111110016303 01 o H20 H20 H C]. H

The products are described by the generic formula C H Cl SO In all cases, the infrared spectrum shows the presence of the OSO group, and the lack of acidic properties establishes the absence of the HOSO group, thereby establishing the products as sultones.

Because of the presence of two double bonds in the starting material, either or both of which can be involved in the reaction of the addition of the SO O bridge, a generic structure cannot reliably be written. However, in the case of the product of 1,2,3,4,7,7-hexachlorobicy clo(2.2.1)heptadiene-2,5 plus oleum or sulfuric anhydride, the product is believed to have the structure:

since the infrared spectrum shows no double bond and a band is present at 1044 cm? similar to the cyclopropane band of 1,2-dichlorocyclopropane.

The reactions are preferably conducted by admixture of the organic starting material with liquid oleum or with gaseous or liquid sulfur trioxide. By oleum is meant sulfuric acid containing free sulfuric anhydride (sulfur trioxide). Sulfur trioxide may be employed in the pure form or complexed with an electron donor (Lewis base) such as chloroethyl ether or dioxane to moderate the reaction and to facilitate handling. A reagent equivalent to oleum may also be employed by admixing a strong dehydrating agent such as phosphorus pentoxide or acetic an'hydride with concentrated sulfuric acid in amounts sufficient to combine with all of the free water present plus part of the Water combined in the sulfuric acid molecules.

The reactions of the invention may be conducted by merely admixing the reactants in the temperature range from about -40 C. to +150 C. At lower temperatures than such, the reaction is very sluggish; at higher temperatures, undesirable side reactions predominate. The admixture may be conducted by adding either reactant to the other. Where sulfur trioxide is employed as one reactant, it may be added either as liquid, as solid polymeric or as gaseous S0 A solvent is not required, it being convenient to employ such as diisopropyl ether or dioxane, or a nitrohydrocarbon such as nitromethane or nitrobenzene, or an anhydride such as acetic anhydride. The last-named type of solvent may also serve in the double role of dehydrating agent for the sulfuric reagent where said sulfuric reagent contains water.

The reaction is conveniently carried out at or near atmospheric pressure, but is also operable at subor superatmospheric pressure. The products of the reaction may be isolated by conventional means such as filtration, extraction, distillation, or sublimation. At suitable concentrations, they will crystallize from the reaction medium and may be isolated by filtration. They may in general be induced to crystallize by dilution of the reaction medium with water and/or cooling. Alternatively, the sultones, being soluble in most organic solvents, may be isolated and separated from impurities such as excess sulfuric acid, by-product sulfonic acids, and the like, by extraction from the reaction mixture by organic solvents. Suitable solvents are, for example, those named above as reaction solvents. The products may be further purified by washing with water, by recrystallization from solvents, by sublimation, and other means known to the art for purification of organic compounds.

The products of the reaction are useful as chemical intermediates, as flame-retardant additives for resins, and as textile treating agents to introduce flame retardancy.

As indicated above, the compositions of this invention exhibit pesticidal activity, and are particularly outstanding as fungicidesj They also possees certain insecticidal activity such as toxicity toward mites and the like, and are active also against bacteria and marine fouling organisms. their halogenation products, thermal decompositon products, hydrogenation products, adducts and products in which the sultone ring has been cleaved or opened by nucleophilic reagents are useful as pesticides, as intermediates for preparing pesticides, or for organic synthesis generally.

In addition to their major advantages of biocidal activity and their availability as biocidal intermediates and chemical intermediates, this invention in its composition aspect offers other additional major advantages.

Forexample, these compositions due to their unique probable structure, stability and solubility in a variety of organic solvents lend themselves to formulation in diverse forms ranging from the simple to the complex. The invention compositions may be utilized as biocides, particularly as fungicides and miticides in the pure form or as reaction crudes. Where they are to be used as intermediates, the purified product is often both necessary and desirable.

The pesticidal preparations are conveniently made up as liquid or as solid formulations. Examples of solid formulations are dusts, wettable powders, granules and pellets. Each of these may contain one or more of the invention compositions combined with a solid carrier or extender, ordinarily a non-reacting or inert substance such as sand, clays, talcs, sawdust, flours, alkaline earth carbonate, oxides, phosphates, and the like as well as diatomaceous earths, micas and similar suitable materials.

Where liquid formulations are desirable, liquid extenders, diluents or carriers of a non-reactive nature are utilized. Examples of such materials are aliphatic alcohols, chlorocarbons, ketones and glycols, aromatic hydrocarbons, petroleum fractions and distillates among many others.

Where it is'desired to use the aforementioned wettable In addition, the compositions of this invention,

powders, or liquid formulations either emulsified, dispersed or suspended in water or other fluid, one or more of a class of materials herein referred to as adjuvants may be incorporated into the powder, dust, or liquid formulation. These materials comprise surface active agents, detergents, wetting agents, solubilizing agents, stabilizers, dispersing agents, suspending agents, emulsifying agents, spreaders, stickers, and conditioning agents generally. These materials through their modifying characteristics facilitate handling and application, and not infrequently, enhance or potentiate the compositions of this invention of their pesticidal activity by mechanisms frequently not well understood.

A satisfactory but not exhaustive list of these substances appears among other places in Soap and Chemical Specialties, volume 31, No. 7, page 61; No. 8, pages 48-61; No. 9, pages 52-67 and No. 10, pages 38-67 (1955). Also, see Bulletin E-607 of the Bureau of Entomology and Plant Quarantine of the United States Department of Agriculture.

An additional advantage of the instant compositions is their compatibility with a variety of biocidal materials. For example, it may frequently be convenient to combine one or more compositions of this invention with one or more adjuvants and carriers with insecticidal materials such as chlordane, benzene hexachlorides, DDT, DDD, the insecticidal carbamates, polychlorinated terpenes, the parathions, methoxychlor, insecticidal phosphates, phosphorothioates, and phosphorodithioates, with other fungicides such as sulfur, quinones, dodecylguanidine, the metal dimethyldithiocarbamates, N-trihalomethylthio 4 cyclohexene-1,2-dicarboximide, N-(trichloromethylthio)phthalimide, heptadecylimidazoline, dinitrocapryl crotonate and various fungicidal zinc, iron, nickel, manganese, copper, lead and mercury salts.

In respect to pesticidal use (fungicidal and/or insecticidal), the preferred method of employing the novel sultones of this invention is to apply the compounds or a formulation thereof to the site of the crop to be protected or to the soil, seeds, roots, foliage, branches or fruit. While the precise rates of application depend upon the type and degree of rates of from 0.1 to 10 pounds per acre will generally be suitable in foliar application, lower rates in seed application down to' one ounce per acre, with higher rates, up to and above one hundred pounds per acre in soil application. While the emphasis in this application has been primarily that of fungicidal treatment of plants, the compounds of this invention used serve equally well as an antimicrobial agent in wood, paper, cloth, leather, stored food products, pulp, plastics, paints and other substances susceptible to deterioration due to microorganisms, and will generally be used at 0.1 ppm. or higher, in the medium to be treated. The compounds also have utility in paints, varnishes, and other coatings for prevention of attack by fungi, mildew, marine fouling organisms, and the like.

The following additional examples are submitted to more clearly illustrate thewo rkings of this invention. Except as indicated in the claims, none of the submitted exemplification is to be construed as limitations of this invention in its composition and process aspects.

Example 1 Ten parts of 1,2,3,4,7,7-hexachlorobicyclo(2.2.1)hep- I tadiene-2,5 and 30 parts of oleum (20% sulfur trioxide) were stirred and warmed to After 15 minutes, the reaction mixture partly solidified. After cooling, it was poured into ice water, the precipitated solids were filtered out and washed with water. The crude solid product was recrystallized from heptane to obtain 6 parts of colorless 5 SO --O linkage, and no bands in the C=C stretching region.

Example 2 To 500 parts of oleum (20% sulfur trioxide) was added 100 parts of S-methylene-l,2,3,4,7,7-hexachlorobicyclo(2.2.'l)-heptene-2 with stirring and cooling to hold the temperature below 50. After stirring for 30 minutes, the thickened mixture was poured into ice water. The precipitated solid was extracted with methylene chloride, the extract was washed with water, dried over magnesium sulfate,'filtered, and diluted with carbon tetrachloride. Upon partial evaporation, 83 parts of colorless crystalline product, M.P. 185'187.5 was obtained as a precipitate. This product, after recrystallization from methylene chloride-carbon tetrachloride, melted at 192.5

Analysis.Calcd. for C H Cl SO C, 24.35; H, 1.27; Cl, 54.0; S, 8.11; M01. Wt. 393. Found: C, 24.35; H, 1.36; Cl, 54.7; S, 7.98; M01 Wt. 423il%.

Example 3 In a manner similar to Example 1, ten parts of Z-methyl 1,4,5,6,7,7 hexachlorobicyclo(2.2.l)heptadiene-2,5 and 30 parts of oleum were reacted to produce a nonacidic solid product having the correct analysis for C H Cl SO and showing bands characteristic of the SO -O linkage in the infared spectrum.

Example 4 Sultone C H Cl SO O Attapulgus clay 43 Lignin sulfonate dispersing agent 5 Sodium alkylaryl sulfonate wetting agent 2 Example 6 An emulsifiable formulation of the sultone C H Cl SO (Example 4) was prepared by blending the following ingredients:

Lbs. sultone CgHgClsSOg 2 Toximul S 0.04 Toximul R 0.04

Xylene, to make 1 gal. total volume.

*Qommercial polyoxyethylene ether alkylaryl sulfonate wetting agents.

Example 7 Tomato plants infested with spores of Alternaria solani (the causative fungal pathogen of early blight disease) were sprayed at various concentrations with the chemicals of the invention. Several infested plants were left unsprayed for comparison. About two weeks later, when the unsprayed plants were exhibiting numerous leaf lesions characteristic of the disease, the control of the disease (reduction in number of lesions) was estimated on the treated tomato plants. The results are as follows:

Disease Control (percent Relative to Untreated) Chemical 400 p.p.m. ppm.

Product of Example 2 100 100 Product of Example 1 100 61 wherein A and B are carbon atoms, D is a hydrogen, lower alkyl, or lower alkylidene radical, E is a hydrogen or lower alkyl radical, A and B being connected by a double bond when D is monovalent and by a single bond when D is divalent, and having a total of n carbon atoms, with a compound chosen from the group consisting of sulfuric anhydride and oleum.

2. A method according to claim 1 in which the sultone is applied to a locus of a fungus.

3. A method according to claim 1 in which the sultone is applied to a locus of an insect.

4. A pesticidal composition comprising a pesticidally effective proportion of a sultone of empirical formula C H Cl SO wherein n is from 7 to 23, prepared by the reaction of the starting compound of the formula:

wherein A and B are carbon atoms, D is selected from the group consisting of hydrogen, lower alkyl and lower alkylidene, E is selected from the group consisting of hydrogen and lower alkyl, A and B being connected by a double bond when D is monovalent and by a single bond when D is divalent, and having a total of n carbon atoms, with a compound selected from the group consisting of sulfuric anhydride and oleum, and a carrier therefor.

5. A pesticidal composition according to claim 4 in which the sultone is of empirical formula C H Cl SO and the carrier is a clay.

6. A pesticidal composition according to claim 4 in which the sultone is of empirical formula C H Cl SO and the carrier is a liquid hydrocarbon.

No references cited.

JULIAN S. LEVITT, Primary Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent N0 3 253 ,983 May 31 1966 Edward D. Weil It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 1, lines 68 to 72, for that portion of the formula reading =CH read =CH column 2 lines 5 to 10, for that portion of the formula reading =CH read =CH line 71, for "S0 read S0 column 5, line 41, for "decompositon" read decomposition column 4, line 75, for "characteristics" read characteristic column 6,

lines 22 to 27 for that portion of the formula reading CX read (.Cl

Signed and sealed this 24th day of October 1967.

EDWARD M .FLETCHER,JR. EDWARD J BRENNER Attesiiing Officer Commissioner of Patents 

1. A METHOD OF CONTROLLING PESTS WHICH COMPRISES APPLYING TO THE LOCUS TO BE TREATED AN EFFECTIVE AMOUNT OF A SULTONE OF EMPIRICAL FORMULA CNH2N-12CL6SO3, WHEREIN N IS FROM 7 TO 23, PREPARED BY THE REACTION OF A STARTING COMPOUND OF THE FORMULA: 